Disperse dyes

ABSTRACT

Disperse dyes of the general formula I  &lt;IMAGE&gt; +TR  &lt;IMAGE&gt;  wherein D signifies a diazo component which is usual with disperse dyes, K signifies an aromatic radical of formula   &lt;IMAGE&gt; (a)  &lt;IMAGE&gt; (b) or  &lt;IMAGE&gt; (c)  Y signifies  &lt;IMAGE&gt;   and the other symbols have the meanings as defined in claim 1, are useful for dyeing or printing hydrophobic, fully or half-synthetic organic fiber materials.

The invention relates to the disperse dyes of the general formula I ##STR4## wherein D signifies a diazo component which is usual with disperse dyes,

K signifies an aromatic radical of formula ##STR5## R₁ signifies hydrogen, chlorine, C₁₋₂ -alkoxy, acylamino, R₂ signifies hydrogen, C₁₋₄ -alkoxyethoxy, chlorine, bromine, or together with R₃ signifies a group of formula --*CH(CH₃)CH₂ C(CH₃)₂ --(*bonded to the nucleus),

R₃ signifies hydrogen, C₁₋₆ -alkyl, C₃₋₄ -alkenyl, chloro-- or bromo-C₃₋₄ -alkenyl, C₃₋₄ -alkinyl, phenyl-C₁₋₃ -alkyl, C₁₋₄ -alkoxycarbonyl-C₁₋₃ -alkyl, allyl, C₁₋₂ -alkoxyethyl, C₃₋₄ -alkenyloxycarbonyl-C₁₋₃ -alkyl, C₃₋₄ alkinyloxycarbonyl-C₁₋₃ -alkyl, phenoxy-C₂₋₄ -alkyl; C₂₋₄ -alkyl substituted by halogen, cyano, C₁₋₄ alkoxy, C₁₋₄ -alkylcarbonyloxy or C₁₋₄ -alkoxycarbonyloxy; or a group of formula --CH₂ --CH(R₈)CH₂ --R₉,

R₄ signifies hydrogen, phenyl or C₁₋₂ -alkyl,

R₅ signifies a radical of formula ##STR6## R₆ signifies hydrogen or hydroxyl, R₇ signifies hydrogen or C₁₋₄ -alkyl,

R₈ signifies hydroxyl, C₁₋₄ -alkylcarbonyloxy or C₁₋₄ -alkoxycabonyloxy,

R₉ signifies chlorine, C₁₋₄ -alkoxy, phenoxy, allyloxy, C₁₋₄ -alkylcarbonyloxy, hydrogen or C₁₋₄ -alkyl,

R₁₀ signifies hydrogen or C₁₋₄ -alkyl,

Y signifies ##STR7## m and z independently signify zero or 1 and n signifies a number from 1 to 5, with the proviso that,

if K is a radical of formula b or c, R₃ signifies hydrogen, and mixtures thereof.

One group of preferred dyestuffs of formula I corresponds to the general formula Ia ##STR8## wherein D₁ is 3-phenyl-1,2,4-thiadiazolyl or corresponds to one of the following formulae: ##STR9## wherein a signifies hydrogen, chlorine, bromine, cyano, nitro-, C₁₋₄ -alkoxycarbonyl, C₁₋₃ -alkylsulphonyl, preferably hydrogen, chlorine, cyano or nitro,

b signifies chlorine, bromine, nitro, methyl, C₁₋₂ -alkylsulphonyl, C₁₋₄ -alkylcarbonyl, aminosulphonyl, mono- or di-C₁₋₄ -alkylaminosulphonyl, phenylaminosulphonyl, C₁₋₄ -alkoxycarbonyl, aminocarbonyl, mono- or di-C₁₋₄ -alkylaminpcarbonyl, phenylaminocarbonyl, phenylazo, benzyloxycarbonyl, tetrahydrofurfuryl-2-oxycarbonyl, C₃₋₄ -alkenyloxycarbonyl, C₃₋₄ -alkinyloxycarbonyl or phenoxycarbonyl, preferably nitro,

c signifies hydrogen or chlorine, or if d is hydrogen, also thiocyano,

d signifies hydrogen, chlorine, bromine or cyano,

e signifies nitro, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkoxycarbonyl, cyano, aminocarbonyl, mono- or di-C₁₋₄ -alkylaminocarbonyl,

f signifies hydrogen, chlorine, bromine, C₁₋₂ -alkyl or phenyl,

g signifies nitro, cyano, formyl, dicyanovinyl or a group of formula --CH═CH--NO₂, --CH═C(CN)CO--OC₁₋₄ -alkyl, H₅ C₆ --N═N-- or 3- or 4NO₂ --C₆ H₄ --N═N--,

h signifies cyano or C₁₋₄ -alkoxycarbonyl,

i signifies C₁₋₄ -alkyl, phenyl or C₁₋₄ -alkylmercapto,

j signifies --CN, --CH═CH₂ or phenyl,

k signifies C₁₋₄ -alkyl,

l signifies hydrogen, chlorine, bromine, cyano, thiocyano, nitro, C₁₋₄ -alkoxycarbonyl, di-C₁₋₄ -alkylaminosulphonyl or formyl,

p signifies hydrogen, chlorine or bromine and

q signifies C₁₋₄ -alkyl, C₁₋₄ -alkoxycarbonyl-C₁₋₄ -alkylene or C₁₋₄ -alkylene-COOCH₂ CF₃,

whereby the phenyl nuclei of these substituents may bear one or two substituents from the series chlorine, bromine, methyl or C₁₋₂ -alkoxy,

R₁ ' signifies hydrogen, C₁₋₂ -alkyl, chlorine or acylamino,

R₂ ' signifies hydrogen, chlorine, C₁₋₂ -alkoxy, C₁₋₂ -alkoxyethoxy, or with R₃, a group of formula --CH(CH₃)CH₂ C(CH₃)₂ --,

R₃ and R₅ have the meanings given above,

R₄ ' and R₁₀ ' independently signify hydrogen or C₁₋₂ -alky and

Y, m, z and n have the above meanings.

Particularly preferred disperse dyes correspond to formula Ib ##STR10## wherein D₂ signifies the radical of a diazo component from the series 2,6-dicyano-4-chloro-, -4-bromo-, -4-methyl- or -4-nitrophenyl, 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or 2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro-, 2-bromo- or 2-cyano-4-nitrophenyl, 2,4-dinitro-5-chlorophenyl or -5-thiocyanophenyl, 2,4-dinitro-5,6-dichlorophenyl, 2,5-dichloro-4-nitrophenyl, 4-nitrophenyl, 4-phenylazophenyl, 4-C₃₋₄ -alkenyloxycarbonylphenyl, 4-C₃₋₄ -alkinyloxycarbonylphenyl, 4-C₁₋₄ -alkoxycarbonylphenyl, 2-C₁₋₄ -alkoxycarbonyl-4-nitrophenyl, 4-phenoxycarbonylphenyl, 4-benzyloxycarbonylphenyl, 4-(tetrahydrofurfuryl-2'-oxycarbonyl)-phenyl, 3,5-dicyano-4-chloro-thienyl-2,3,5-dicyano-thienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitro-thienyl-2,3,5-dinitro-thienyl-2,3-(C₁₋₄ -alkoxycarbonyl)-5-nitro-thienyl-2,5-phenylazo-3-cyanothienyl-2,5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitro-thiazolyl-2,5-nitrobenzisothiazolyl-3,3-methyl-4-cyano-isothiazolyl-5,3-phenyl-1,2,4-thiadiazolyl-2,5-(C₁₋₂ -alkylmercapto)-1,3,4-thiadiazolyl-2,3-C₁₋₂ -alkoxycarbonylethylmercapto-1,2,4-thiadiazolyl-5,1-cyanomethyl-4,5-dicyano-imidazolyl-2,6-nitrobenzothiazolyl-2,5-nitrobenzothiazolyl-2, 6-thiocyanobenzothiazolyl-2,6-chlorobenzothiazolyl-2,(5),6, (7)-dichlorobenzothiazolyl-2, phthalidyl-5 or of formula ##STR11## in which B signifies oxygen or a group of formula ##STR12## and the symbols R₁ ', R₂ ', R₃, R₄ ', R₅, R₁₀ ', m and n are defined as above.

Furthermore, particular preference is given to the disperse dyes of formula Ib, wherein

D₂ signifies the radical of a diazo compound of formula 2,6-dicyano-4-chloro, -4-bromo, -4-methyl or -4-nitro-phenyl, 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or 2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro-, 2-bromo- or 2-cyano-4-nitrophenyl, 2,4-dinitro-5-chlorophenyl or -5-thiocyanophenyl, 2,4-dinitro-5,6-dichiorophenyl, 2,5-dichloro-4-nitrophenyl, 4-nitrophenyl or phthalidyl-5,

R₁ ' signifies hydrogen, methyl or acylamino,

R₂ ' signifies hydrogen, C₁₋₂ -alkoxy or C₁₋₂ -alkoxyethoxy,

R₃ signifies hydrogen, C₁₋₄ -alkyl, allyl, C₁₋₂ -alkoxyethyl, C₁₋₂ -alkoxycarbonyloxyethyl or C₁₋₂ -alkylcarbonyloxyethyl,

R₄ ' signifies hydrogen,

R₅ signifies a radical as above defined,

R₁₀ ' signifies hydrogen

m signifies 0 or 1 and

n signifies 1 or 2.

Other suitable dyes of formula Ib, are those wherein

D₂ signifies a diazo component from the series 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2,4-dinitro-5-chloro- or -5-thiocyanophenyl or 2,4-dinitro-5,6-dichlorophenyl,

R₁ ' signifies C₁₋₂ -alkylcarbonylamino,

R₂ ' signifies C₁₋₂ -alkoxy or C₁₋₂ -alkoxyethoxy,

R₃ signifies hydrogen, C₁₋₄ -alkyl, cyanoethyl, C₁₋₂ -alkoxyethyl, C₃₋₄ -alkenyl, C₁₋₂ -alkylcarbonyloxyethyl, chlorallyl, C₃₋₄ -alkinyl, C₁₋₂ -alkoxycarbonylmethyl, allyloxycarbonylmethyl or propargyloxycarbonylmethyl,

R₄ ' signifies hydrogen or methyl and

R₅, R₁₀ ', m and n have the meanings given above.

Further suitable dyes of formula Ib, are those wherein

D₂ signifies a diazo component from the series 4-nitrophenyl, 2-chloro-4-nitrophenyl, 2-bromo-4-nitrophenyl, 2,6-dichloro-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl or 2-cyano-4-nitrophenyl,

R₁ ' signifies hydrogen or methyl,

R₂ ' signifies hydrogen,

R₃ ' signifies C₁₋₄ -alkyl

R₄ ' signifies hydrogen or methyl,

R₅ signifies a radical as above defined,

R₁₀ ' signifies hydrogen

m signifies zero or 1, and

n signifies 1.

Still further suitable dyes of the present invention are those corresponding to formula Ic, ##STR13## wherein D₂ signifies the radical of a diazo compound of formula 2,6-dicyano-4-chloro, -4-bromo, -4-methyl or -4-nitro-phenyl, 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or 2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro-, 2-bromo- or 2-cyano-4-nitrophenyl, 2,4-dinitro-5-chlorophenyl or -5-thiocyanophenyl, 2,4-dinitro-5,6-dichlorophenyl, 2,5-dichloro-4-nitrophenyl, 4-nitrophenyl or phthalidyl-5

and the symbols R₁ ', R₂ ', R₃, R₄ ', R₅, R₁₀ ', m and n are defined as above.

The diazo components may be all mono- to bi-nuclear, carbocyclic or heterocyclic organic radicals of aromatic character, which may bear substituents that are conventional in the case of disperse dyes. Water-solubilizing substituents are excluded in particular, that is especially sulphonic acid groups. The diazo components may also be radicals of monoazo compounds. Examples of diazo components are: phenyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrazolyl, imidazolyl, triazolyl, benzothiazolyl or benzisothiazolyl radicals, which preferably bear substituents as indicated from the above meanings of D₁.

The substituents on these nuclei may be in particular halogen atoms, especially chlorine or bromine atoms, nitro, cyano, thiocyano, hydroxyl, alkyl, alkoxy, phenyl, phenoxy and acyl groups, as well as especially also on the thienyl or thiazolyl diazo components, formyl and radicals of formulae --CH═CH--NO₂, --CH═C(CN)₂ and --CH═C(CN)acyl.

Preferred acyl groups correspond to formula E-Z in which

E signifies hydrogen or a hydrocarbon radical which may bear the abovementioned substituents and/or may contain hetero atoms, preferably an optionally substituted alkyl or phenyl radical and

Z signifies a radical --O--CO--, --SO₂ --, --O--SO₂ --, --CO--, --NE--CO-- or --NE--SO₂ --.

If not otherwise stated, all the said alkyl and alkoxy groups contain 1 to 8, especially 1 to 4 carbon atoms. They may be straight-chain or branched, and bear as substituents e.g. halogen atoms, preferably fluorine or chlorine atoms, hydroxy, alkoxy, phenyl, phenoxy, cyano, thiocyano, acyl, acyloxy or acylamino groups.

All the said phenyl radicals (also phenoxy and phenylazo radicals) may be further substituted, e.g. by halogen atoms (preferably chlorine or bromine atoms), alkyl, alkoxy, nitro, cyano, thiocyano, acyl, acyloxy or acylamino groups.

If not indicated to the contrary, all alkyl, alkylene and alkenyl radicals are straight-chain.

Production of the new dyestuffs of formula I is characterized in that a diazotized amine of formula II

    D--NH.sub.2                                                (II)

is coupled with a compound of formula III ##STR14## Diazotization and coupling are effected according to generally known methods.

The compounds of formulae II and III are known, or may be easily produced from known compounds according to methods known to a person skilled in the art.

Dyestuffs of formula I in which D corresponds to the formula ##STR15## where a and/or d are a cyano radical, can also be prepared by cyano-exchange from the corresponding halogen substituted dyestuffs, such a method is known to the skilled person.

Dyestuffs of formula I in which m is 1 and D corresponds to the formula ##STR16## wherein the symbols a, b, c und d have the above meanings can also be made by reacting ##STR17## with a compound of the following formula ##STR18## wherein Hal is preferably chlorine or bromine and the symbols R₄, R₁₀, R₅, n and z have the above defined meanings. Such a method is known to the skilled man.

From an aqueous suspension, the new dyestuffs of formula I are absorbed in an excellent manner on textile material consisting of fully synthetic or semi-synthetic, hydrophobic, high molecular weight organic material. They are especially suitable for dyeing or printing textile material consisting of linear, aromatic polyesters, as well as cellulose-21/2-acetate and cellulose triacetate.

Dyeing or printing are effected in accordance with known processes, e.g. those described in French Patent Specification no. 1,445,371.

The dyeings obtained have good all-round fastnesses; in addition to the particularly good fastness to thermomigration, also notable are the light fastness, thermofixation fastness and pleating fastness, as well as the excellent wet fastness, following thermal fixation (especially the M&S C4A wash).

They are also suitable for thermo transfer printing processes.

In the following examples, the parts and percentages are by weight. The temperatures are given in degrees celsius.

EXAMPLE 1

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 100 parts of cold sulfuric acid (93%) and mixed at 0° to 5° over the course of 30 minutes with 32 parts of nitrosylsulphuric acid (40%). Stirring continues for 3 to 4 hours at 0° to 5° and then the diazonium salt solution obtained is poured whilst stirring into a mixture of 35.2 parts of 2-(N-methyl-N-phenylamino)-propionic acid-2'-N-phthalimidoethylester, 100 parts of glacial acetic acid, 2 parts of amidosulphonic acid, 200 parts of water and 500 parts of ice. The precipitated dyestuff is filtered off, washed with water until free from acid and dried in a vacuum at 60°. The resultant dyestuff corresponds to formula ##STR19##

It dyes polyester fibre material in ruby-red shades with excellent fastness, in particular very good wet fastness after thermal fixing, and is eminently suitable for the modern rapid-dyeing processes, for example the ®Foron-RD process. λ_(max). =519 nm(DMF).

EXAMPLE 2

The process is as described in example 1, but the 35.2 parts of 2-(N-methyl-N-phenylamino)-propionic acid-(2'-N-phthalimido)ethylester are replaced by 41.0 parts of 2-(N-methyl-N-phenylamino)-propionic acid-(2'-N-phthalimidoethoxycarbonyl)methylester. The resultant dyestuff corresponds to formula ##STR20##

It dyes polyester fibre material in ruby-red shades with excellent fastness, in particular very good wet fastness after thermal fixing. λ_(max). =516 nm (DMF).

EXAMPLE 3

The process is as described in example 1, but the 35.2 parts of 2-(N-methyl-N-phenylamino)-propionic acid-2'-N-phthalimidoethylester are replaced by 38.8 parts of 2-(N-methyl-N-phenylamino)-propionic acid-2'-N-o-sulphobenzimidoethylester. The resultant dyestuff corresponds to formula ##STR21##

It dyes polyester fibre materials in ruby-red shades with excellent fastness, in particular very good wet fastness, after thermal fixing. λ_(max). =522 nm (DMF).

EXAMPLE 4

20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene are stirred into 100 parts of sulfuric acid (93%) and mixed at 30° over the course of one hour with 32 parts of nitrosylsulphuric acid (40%). Stirring is effected for 2-3 hours at 30°-32°, and then the diazonium salt solution obtained is added in drops whilst stirring to a mixture of 35.2 parts of 2-(N-methyl-N-phenylamino)-propionic acid-2'-N-phthalimidoethylester, 100 parts of glacial acetic acid, 2 parts of amidosulphonic acid, 200 parts of water and 500 parts of ice. The precipitated dyestuff is filtered off, washed with water until free from acid, and dried in a vacuum at 60°. It corresponds to formula ##STR22## and dyes polyester fibre material in yellow-brown shades with excellent fastness, inparticular very good wet fastness, after thermal fixing. λ_(max). (DMF)=431 nm.

The dyes of the following table 1 are made according to Example 1 using the corresponding starting materials and have the following formula: ##STR23##

                                      TABLE 1                                      __________________________________________________________________________                                                         Shade  λmax         Ex.                                                 on     (DMF)               No.                                                                               DK           R.sub.1                                                                               R.sub.2                                                                             R.sub.3      m  n  Q    PES    nm                  __________________________________________________________________________      5                                                                                             H      H    CH.sub.3     0  3                                                                                  ##STR24##                                                                          ruby   521                  6 "            CH.sub.3                                                                              H    H            0  2                                                                                  ##STR25##                                                                          "      523                  7 "            NHCOCH.sub.3                                                                          H    H            0  2  "    "      538                  8 "            "      H    H            0  2                                                                                  ##STR26##                                                                          "      537                  9 "            H      H    CH.sub.3     1  3  "    "      517                 10 "            H      Cl   H            0  2  "    scarlet                                                                               481                 11                                                                                 ##STR27##   H      H    CH.sub.3     0  2                                                                                  ##STR28##                                                                          orange 474                 12 "            H      H    "            0  2                                                                                  ##STR29##                                                                          "      474                 13 "            H      H    "            1  2  "    "      469                 14 "            H      H    "            1  2                                                                                  ##STR30##                                                                          orange 469                 15 "            H      H    "            1  3  "    "      470                 16 "            H      H    C.sub.2 H.sub.5                                                                             1  2  "    "      474                 17 "            H      H    "            1  3  "    "      474                 18 "            H      H    "            1  2                                                                                  ##STR31##                                                                          "      475                 19                                                                                 ##STR32##   H      Cl   CH.sub.3     0  2                                                                                  ##STR33##                                                                          gold-yellow                                                                           438                 20                                                                                 ##STR34##   NHCOCH.sub.3                                                                          OCH.sub.3                                                                           H            0  2  "    marine                                                                                585e                21 "            "      "    H            0  2                                                                                  ##STR35##                                                                          "      583                 22 "            "      "    H            1  2  "    "      581                 23 "            "      "    H            1  2                                                                                  ##STR36##                                                                          "      583                 24                                                                                 ##STR37##   NHCOCH.sub.3                                                                          OCH.sub.3                                                                           H            1  3                                                                                  ##STR38##                                                                          marine                                                                                584e                25 "            "      OC.sub.2 H.sub.5                                                                    H            1  2                                                                                  ##STR39##                                                                          "      582                 26                                                                                 ##STR40##   H      H    CH.sub.3     0  2  "    yellow-brown                                                                          431                 27 "            H      H    C.sub.2 H.sub.5                                                                             0  2  "    "      434                 28                                                                                 ##STR41##   H      H    CH.sub.3     1  2                                                                                  ##STR42##                                                                          yellow-brown                                                                          429                 29 "            H      H    "            1  2                                                                                  ##STR43##                                                                          "      429                 30 "            H      H    "            1  3  "    "      430                 31                                                                                 ##STR44##   H      H    "            0  2  "    red    519                 32 "            H      H    "            0  3  "    "      520                 33                                                                                 ##STR45##   H      H    CH.sub.3     0  2                                                                                  ##STR46##                                                                          red    519                 34                                                                                 ##STR47##   H      H    "            0  2  "    violet 562                 35 "            H      H    "            0  2                                                                                  ##STR48##                                                                          "      562                 36                                                                                 ##STR49##   NHCOCH.sub.3                                                                          Cl   H            1  2                                                                                  ##STR50##                                                                          scarlet                                                                               494                 37 "            "      Cl   H            1  2                                                                                  ##STR51##                                                                          "      494                 38 "            "      Cl   H            1  3                                                                                  ##STR52##                                                                          "      495                 39 "            H      H    CH.sub.3     1  2  "    "      496                 40 "            H      H    "            1  2  "    "      496                 41                                                                                 ##STR53##   H      H    "            0  2  "    gold-yellow                                                                           442                 42                                                                                 ##STR54##   H      H    C.sub.2 H.sub.5                                                                             0  2                                                                                  ##STR55##                                                                          gold-yellow                                                                           448                 43 "            CH.sub.3                                                                              H    CH.sub.3     0  2  "    "      448                 44 "            "      H    "            0  2                                                                                  ##STR56##                                                                          "      448                 45 "            H      H    "            0  2  "    "      448                 46 "            CH.sub.3                                                                              H    "            1  2                                                                                  ##STR57##                                                                          "      443                 47                                                                                 ##STR58##   NHCOCH.sub.3                                                                          OCH.sub.3                                                                           H            0  2                                                                                  ##STR59##                                                                          marine-blue                                                                           584                 48                                                                                 ##STR60##   CH.sub.3                                                                              OCH.sub.3                                                                           CH.sub.3     1  2                                                                                  ##STR61##                                                                          violet 560                 49                                                                                 ##STR62##   "      "    "            1  2  "    blue   600                 50                                                                                 ##STR63##   NHCOCH.sub.3                                                                          OCH.sub.3                                                                           H            1  2                                                                                  ##STR64##                                                                          marine-blue                                                                           581                 51                                                                                 ##STR65##   NHCOCH.sub.3                                                                          OCH.sub.3                                                                           H            1  3                                                                                  ##STR66##                                                                          marine-blue                                                                           582                 52 "            "      "    H            1  2                                                                                  ##STR67##                                                                          "      581                 53                                                                                 ##STR68##   H      H    CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               0  2                                                                                  ##STR69##                                                                          red    513                 54 "            H      H    C.sub.2 H.sub.5                                                                             1  2  "    ruby   520                 55 "            H      H    CH.sub.2 CHCH.sub.2                                                                         0  2  "    red    515                 56                                                                                 ##STR70##   H      H    C.sub.2 H.sub.5                                                                             0  2                                                                                  ##STR71##                                                                          ruby   525                 57                                                                                 ##STR72##   H      H    "            0  2                                                                                  ##STR73##                                                                          yellow-brown                                                                          434                 58 "            H      H    "            1  2  "    "      432                 59                                                                                 ##STR74##   CH.sub.3                                                                              OCH.sub.3                                                                           CH.sub.3     0  2  "    blue   603                 60                                                                                 ##STR75##   CH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                             0  2                                                                                  ##STR76##                                                                          violet 589                 61                                                                                 ##STR77##   H      H    C.sub.2 H.sub.5                                                                             0  2  "    marine-blue                                                                           613                 62                                                                                 ##STR78##   H      H    "            0  2  "    red    540                 63                                                                                 ##STR79##   H      H    CH.sub.2 CH.sub.2 CN                                                                        0  2  "    scarlet                                                                               501                 64                                                                                 ##STR80##   CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                             0  2                                                                                  ##STR81##                                                                          marine-blue                                                                           592                 65                                                                                 ##STR82##   "      H    "            0  2  "    scarlet                                                                               500                 66                                                                                 ##STR83##   H      H    CH.sub.2 CH.sub.2 OCOOCH.sub.3                                                              0  2  "    red    514                 67                                                                                 ##STR84##   H      H    CH.sub.3     0  2                                                                                  ##STR85##                                                                          yellow-brown                                                                          430                 68                                                                                 ##STR86##   H      H    CH.sub.3     0  2  "    ruby   512                 69                                                                                 ##STR87##   H      H    "            0  3  "    "      514                 70 "            H      H    "            1  2  "    red    509                 71                                                                                 ##STR88##   NHCOCH.sub.3                                                                          H    C.sub.2 H.sub.5                                                                             0  2                                                                                  ##STR89##                                                                          blueish                                                                               531                 72                                                                                 ##STR90##   CH.sub.3                                                                              OCH.sub.3                                                                           CH.sub.3     1  3  "    blue   601                 73 "            "      "    "            1  2                                                                                  ##STR91##                                                                          "      602                 74 "            NHCOCH.sub.3                                                                          "    H            0  2                                                                                  ##STR92##                                                                          "      611                 75                                                                                 ##STR93##   NHCOCH.sub.3                                                                          "    CH.sub.2CHCHCl                                                                              0  2                                                                                  ##STR94##                                                                          blue   621                 76 "            "      "    CH.sub.2 CHCH.sub.2                                                                         0  2  "    "      625                 77 "            "      "    C.sub.3 H.sub.7 -n                                                                          1  2  "    "      608                 __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR95##                                                                                                       Shade  λmax                           Ex.                               on     (DMF)                                 No.                                                                               DK        R.sub.1                                                                            R.sub.2                                                                          R.sub.3                                                                            m  n  Q    PES    nm                                    __________________________________________________________________________     78                                                                                 ##STR96##                                                                               H   H C.sub.2 H.sub.5                                                                    0  2                                                                                  ##STR97##                                                                          ruby   521                                   79 "         CH.sub.3                                                                           H CH.sub.3                                                                           0  2  "    "      529                                   80 "         H   H C.sub.2 H.sub.5                                                                    0  2                                                                                  ##STR98##                                                                          "      521                                   81                                                                                 ##STR99##                                                                               H   H C.sub.2 H.sub.5                                                                    1  3                                                                                  ##STR100##                                                                         ruby   518                                   82                                                                                 ##STR101##                                                                              H   H CH.sub.3                                                                           0  2  "    yellow-brown                                                                          429                                   83                                                                                 ##STR102##                                                                              H   H "   0  2                                                                                  ##STR103##                                                                         orange 472                                   84 "         H   H C.sub.2 H.sub.5                                                                    1  2  "    "      473                                   85                                                                                 ##STR104##                                                                              H   Cl                                                                               H   1  2                                                                                  ##STR105##                                                                         scarlet                                                                               480                                   86 "         H   Cl                                                                               H   0  2                                                                                  ##STR106##                                                                         "      483                                   87 "         H   Cl                                                                               H   1  2  "    "      480                                   88 "         H   Cl                                                                               H   1  2                                                                                  ##STR107##                                                                         "      483                                   89                                                                                 ##STR108##                                                                              H   H CH.sub.3                                                                           0  2                                                                                  ##STR109##                                                                         bordeaux red                                                                          516                                   __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________                                                           λmax              Ex.                                            Shade  (DMF)                    No.                                                                               Formula                                     on PES nm                       __________________________________________________________________________     90                                                                                 ##STR110##                                 marine blue                                                                           590                      91                                                                                 ##STR111##                                 "      591                      92                                                                                 ##STR112##                                 blue   609                      93                                                                                 ##STR113##                                 "      610                      94                                                                                 ##STR114##                                 blueish violet                                                                        570                      __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR115##                                                                                                                        Shade λmax          Ex.                                                 on    (DMF)                No. DK           R.sub.1 R.sub.2                                                                             R.sub.3                                                                             R.sub.4                                                                             R.sub.10                                                                           m Q     PES   nm                   __________________________________________________________________________     95                                                                                  ##STR116##  H       H    CH.sub.3                                                                            CH.sub.3                                                                            H   1                                                                                 ##STR117##                                                                          orange                                                                               470                  96  "            H       H    "    --   CH.sub.3                                                                           0 "     "     475                  97                                                                                  ##STR118##  H       H    "    CH.sub.3                                                                            H   1                                                                                 ##STR119##                                                                          ruby  520                  98                                                                                  ##STR120##  H       H    CH.sub.3                                                                            H    CH.sub.3                                                                           1                                                                                 ##STR121##                                                                          ruby  517                  99                                                                                  ##STR122##  NHCOCH.sub.3                                                                           OCH.sub.3                                                                           H    --   CH.sub.3                                                                           0 "     marine                                                                               586e                 100                                                                                 ##STR123##  CH.sub.3                                                                               OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                     --   H   0                                                                                 ##STR124##                                                                          blue  666                  __________________________________________________________________________

APPLICATION EXAMPLE

The dyestuff obtained according to example 1 is converted by means of sand-grinding in the presence of dispersing agents, e.g. commercial lignin sulphonate, with subsequent fine disintegration, into an ultra-disperse dye preparation having an average particle size of 1 μm and a dilution ratio of 3:5:10.

12 parts of this preparation are made into a dispersion with 1000 parts of water, and added to the circulating liquor (13,000 parts, containing 30 parts of ammonium sulphate and 0.3 parts of formic acid as a buffer and optionally a carrier/levelling agent combination) at 60° C. The pre-cleaned, compressed, cross-wound spool (1000 parts of polyester yarn on a plastic sleeve) is introduced, the dyeing autoclave closed, and heated in 35 minutes to 130° C. After 90 minutes, cooling is effected to 80° C., the exhausted liquor is drained, and the substrate thus dyed is washed thoroughly with cold water, and purified by reduction in the usual manner. It is then centrifuged and dried. A level, pure, deep ruby-red dyeing is obtained.

Dyeing of polyester yarn can be carried out analogously with examples 2-100, whereby yielding a level, deep dyeing. 

I claim:
 1. A disperse dye of the general formula I ##STR125## wherein D signifies a diazo component which is usual with disperse dyes,K signifies an aromatic radical of formula ##STR126## R₁ signifies hydrogen, chlorine, C₁₋₂ -alkyl, C₁₋₂ -alkoxy or acylamino, R₂ signifies hydrogen, C₁₋₄ -alkoxy, C₁₋₂ -alkoxyethoxy, chlorine, bromine, or together with R₃ signifies a group of formula --*CH(CH₃)CH₂ C(CH₃)₂ --(* bonded to the nucleus), R₃ signifies hydrogen, C₁₋₆ -alkyl, C₃₋₄ -alkenyl, chloro- or bromo-C₃₋₄ -alkenyl, C₃₋₄ -alkinyl, phenyl-C₁₋₃ -alkyl, C₁₋₄ -alkoxycarbonyl-C₁₋₃ -alkyl, allyl or C₁₋₂ -alkoxyethyl,C₃₋₄ -alkenyloxycarbonyl-C₁₋₃ -alkyl, C₃₋₄ -alkinyloxycarbonyl-C₁₋₃ -alkyl, phenoxy-C₂₋₄ -alkyl; C₂₋₄ -alkyl substituted by halogen, cyano, C₁₋₄ -alkoxy, C₁₋₄ -alkylcarbonyloxy or C₁₋₄ -alkoxycarbonyloxy or a group of formula --CH₂ --CH(R₈)CH₂ --R₉, R₄ signifies hydrogen, phenyl or C₁₋₂ -alkyl, R₅ signifies a radical of formula ##STR127## R₆ signifies hydrogen or hydroxyl, R₇ signifies hydrogen or C₁₋₄ -alkyl, R₈ signifies hydroxyl, C₁₋₄ -alkylcarbonyloxy or C₁₋₄ -alkoxycarbonyloxy, R₉ signifies chlorine, C₁₋₄ -alkoxy, phenoxy, allyloxy, C₁₋₄ -alkylcarbonyloxy, hydrogen or C₁₋₄ -alkyl, R₁₀ signifies hydrogen or C₁₋₄ -alkyl, Y signifies ##STR128## m and z independently signify zero or 1 and n signifies a number from 1 to 5, with the proviso that, if K is a radical of formula b or c, R₃ signifies hydrogen, and mixtures thereof.
 2. A disperse dye according to claim 1, having the general formula Ia ##STR129## wherein D₁ is 3-phenyl-1,2,4-thiadiazolyl or corresponds to one of the following formulae: ##STR130## wherein a signifies hydrogen, chlorine, bromine, cyano, nitro-, C₁₋₄ -alkoxycarbonyl C₁₋₃ -alkylsulphonyl, preferably hydrogen, chlorine, cyano or nitro,b signifies chlorine, bromine, nitro, methyl, C₁₋₂ -alkylsulphonyl, C₁₋₄ -alkylcarbonyl, aminosulphonyl, mono- or di-C₁₋₄ -alkylaminosulphonyl, phenylaminosulphonyl, C₁₋₄ -alkoxycarbonyl, aminocarbonyl, mono- or di-C₁₋₄ -alkylaminocarbonyl, phenylaminocarbonyl, phenylazo, benzyloxycarbonyl, tetrahydrofurfuryl-2-oxycarbonyl, C₃₋₄ -alkenyloxycarbonyl, C₃₋₄ -alkinyloxycarbonyl or phenoxycarbonyl, preferably b is nitro, c signifies hydrogen or chlorine, or if d is hydrogen, also thiocyano, d signifies hydrogen, chlorine, bromine or cyano, e signifies nitro, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkoxycarbonyl, cyano, aminocarbonyl, mono- or di-C₁₋₄ -alkylaminocarbonyl, f signifies hydrogen, chlorine, bromine, C₁₋₂ -alkyl or phenyl, g signifies nitro, cyano, formyl, dicyanovinyl or a group of formula --CH═CH--NO₂, --CH═C(CN)CO--OC₁₋₄ -alkyl, H₅ C₆ --N═N-- or 3-- or 4-NO₂ --C₆ H₄ --N═N--, h signifies cyano or C₁₋₄ -alkoxycarbonyl, i signifies C₁₋₄ -alkyl, phenyl or C₁₋₄ -alkylmercapto, j signifies --CN, --CH═CH₂ or phenyl, k signifies C₁₋₄ -alkyl, l signifies hydrogen, chlorine, bromine, cyano, thiocyano, nitro, C₁₋₄ -alkoxycarbonyl, di-C₁₋₄ -alkylaminosulphonyl or formyl, p signifies hydrogen, chlorine or bromine and q signifies C₁₋₄ -alkyl, C₁₋₄ -alkoxycarbonyl-C₁₋₄ -alkylene or C₁₋₄ -alkylene-COOCH₂ CF₃, whereby the phenyl nuclei of these substituents may bear one or two substituents from the series chlorine, bromine, methyl or C₁₋₂ -alkoxy, R₁ ' signifies hydrogen, C₁₋₂ -alkyl, chlorine or acylamino, R₂ ' signifies hydrogen, chlorine, C₁₋₂ -alkoxy, C₁₋₂ -alkoxyethoxy, or with R₃, a group of formula --CH(CH₃)CH₂ C(CH₃)₂ --, R₄ ' and R₁₀ ' independently signify hydrogen or C₁₋₂ -alkyl and R₃, R₅, Y, m, z and n have the same meanings as in claim 1 above.
 3. A disperse dye according to claim 1 having the formula Ib ##STR131## wherein D₂ signifies the radical of a diazo component from the series 2,6-dicyano-4-chloro-, -4-bromo-, -4-methyl- or -4-nitrophenyl, 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or 2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro-, 2-bromo- or 2-cyano-4-nitrophenyl, 2,4-dinitro-5-chlorophenyl or -5-thiocyanophenyl, 2,4-dinitro-5,6-dichlorophenyl, 2,5-dichloro-4-nitrophenyl, 4-nitrophenyl, 4-phenylazophenyl, 4-C₃₋₄ -alkenyloxycarbonylphenyl, 4-C₃₋₄ -alkinyloxycarbonylphenyl, 4-C₁₋₄ -alkoxycarbonylphenyl, 2-C₁₋₄ -alkoxycarbonyl-4-nitrophenyl, 4phenoxycarbonylphenyl, 4-benzyloxycarbonylphenyl, 4-(tetrahydrofurfuryl-2'-oxycarbonyl)-phenyl, 3,5-dicyano-4-chloro-thienyl-2,3,5-dicyano-thienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitro-thienyl-2,3,5-dinitro-thienyl-2,3-(C₁₋₄ -alkoxycarbonyl)-5-nitro-thienyl-2,5-phenylazo-3-cyanothienyl-2,5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitro-thiazolyl-2,5-nitrobenzisothiazolyl-3,3-methyl-4-cyano-isothiazolyl-5,3-phenyl-1,2,4-thiadiazolyl-2,5-(C₁₋₂ -alkylmercapto)-1,3,4-thiadiazolyl-2,3-C₁₋₂ -alkoxycarbonylethylmercapto-1,2,4-thiadiazolyl-5,1-cyanomethyl-4,5-dicyano-imidazolyl-2,6-nitrobenzothiazolyl-2,5-nitrobenzothiazolyl-2,6-thiocyanobenzothiazolyl-2,6-chlorobenzothiazolyl-2,(5),6,(7)-dichlorobenzothiazolyl-2, phthalidyl-5 or of formula ##STR132## wherein B signifies oxygen or a group of formula ##STR133## R₁ ' signifies hydrogen, C₁₋₂ -alkyl, chlorine or acylamino, R₂ ' signifies hydrogen, chlorine, C₁₋₂ -alkoxy, C₁₋₂ -alkoxyethoxy, or with R₃, a group of formula

    --CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.2 --,

R₄ ' and R₁₀ ' independently signify hydrogen or C₁₋₂ -alkyl R₅ signifies a radical of formula ##STR134## m signifies zero or 1, n signifies a number from 1 to
 5. 4. A disperse dye having the formula Ib as claimed in claim 2, whereinD₂ signifies the radical of a diazo compound of formula 2,6-dicyano-4-chloro, -4-bromo, 4-methyl or -4-nitro-phenyl, 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dichloro- or 2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro-, 2-bromo- or 2-cyano-4-nitrophenyl, 2,4-dinitro-5-chlorophenyl or -5-thiocyanophenyl, 2,4-dinitro-5,6-dichlorophenyl, 2,5-dichloro-4-nitrophenyl, 4-nitrophenyl or phthalidyl-5, R₃ signifies hydrogen, C₁₋₄ -alkyl, allyl, C₁₋₂ -alkoxyethyl, C₁₋₂ -alkoxycarbonyloxyethyl or C₁₋₂ -alkylcarbonyloxyethyland the symbols R₅, m and n are defined as in claim 1 and R₁ ', R₂ ', R₄ ' and R₁₀ ' are as defined in claim
 2. 5. A disperse dye having the formula Ib as claimed in claim 2, whereinD₂ signifies the radical of a diazo compound of formula 2,6-dicyano-4-chloro, -4-bromo, -4-methyl or -4-nitrophenyl, 2,4-dinitro-6-chloro-, -6-bromo- or -6-cyanophenyl, 2-chloro- or 2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl, 2,6-dihloro- or 2,6-dibromo-4-nitrophenyl, 2-chloro-4-nitro-6-bromophenyl, 2-chloro-, 2-bromo- or 2-cyano-4-nitrophenyl, 2,4-dinitro-5-chlorophenyl or -5-thiocyanophenyl, 2,4-dinitro-5,6-dichlorophenyl, 2,5-dichloro-4-nitrophenyl, -4-nitrophenyl or phthalidyl-5 R₁ ' signifies hydrogen, methyl or acylamino, R₂ ' signifies hydrogen, C₁₋₂ -alkoxy or C₁₋₂ -alkoxyethoxy, R₃ signifies hydrogen, C₁₋₂ -alkyl, allyl, C₁₋₂ -alkoxyethyl, C₁₋₂ -alkoxycarbonyloxyethyl or C₁₋₂ -alkylcarbonyloxyethyl R₄ ' signifies hydrogen R₅ signifies a radical formula ##STR135## R₁₀ ' signifies hydrogen m signifies 0 or 1 and n signifies 1 or
 2. 6. Process for the production of the dyes of formula I as claimed in claim 1, characterized in that a diazotized amine of formula II

    D--NH.sub.2                                                (II)

is coupled with a compound of formula III ##STR136## wherein Y, m, n, R₃, R₄, R₅ and R₁₀ have the meanings given in claim
 1. 7. Process for the production of the dyes of formula Ia as claimed in claim 2, wherein D corresponds to the formula ##STR137## where a and/or d are a cyano radical, wherein the corresponding halogen substituted dyes are subjected to cyano-exchange.
 8. A method of dyeing or printing, fibres or threads or materials produced therefrom, said fibres, threads or materials produced therefrom comprising fully or semi-synthetic, hydrophobic, high molecular weight organic materials, said method comprising use of at least one of the dyes as claimed in any one of claims 1 to 5 above.
 9. A method of claim 8 wherein the printing comprises transfer printing.
 10. Textile which has been dyed or printed with a disperse dye of formula I or mixtures thereof, as claimed in claim
 1. 11. Disperse dye of Formula I obtainable by a process according to claim
 6. 12. Disperse dye of Formula I obtainable by a process according to claim
 7. 